X-ray diffraction and ^{57}Fe Mössbauer spectroscopy were applied as complementary methods to investigate the structure and hyperfine interactions of the Aurivillius compounds prepared by mechanical activation and subsequent heat treatment. Preliminary milling of precursors enhanced the diffusion process and pure Aurivillius compounds were obtained at lower temperature as compared with conventional solid-state sintering technology (lower at least by 50 K). All the investigated Aurivillius compounds are paramagnetic materials at room temperature.